Infrared signatures of the NCCO radical

文献情報

出版日 2009-09-28

DOI 10.1039/B912803D

インパクトファクター 3.676

著者

Peter R. Schreiner, Hans Peter Reisenauer, Edit Mátyus, Attila G. Császár, Ali Siddiqi, Andrew C. Simmonett, Wesley D. Allen

原文を見る

要旨

The first definitive infrared signatures of the elusive NCCO radical have been measured using a microwave discharge technique combined with low-temperature matrix-isolation spectroscopy, resulting in a consistent set of vibrational assignments for six isotopologues. The infrared spectra of these NCCO isotopologues were concomitantly established by rigorous variational nuclear-motion computations based on a high-level coupled-cluster quartic vibrational force field [ROCCSD(T)/cc-pCVQZ] and cubic dipole field [ROCCSD/cc-pCVTZ]. Our experimental and theoretical results for NCCO overturn the vibrational assignments in a NIST-JANAF compilation and those from a recent two-dimensional cross-spectral correlation analysis. For the parent isotopologue at 11 K in a nitrogen matrix, we find the signature bands ν2(CO str.) = 1889.2 cm−1 and ν3(CC str.) = 782.0 cm−1. Our variational vibrational computations reveal strong mixing of the ν3 stretching fundamental and the ν4 + ν5 bending combination level for all isotopologues. These Fermi resonances manifest a clear breakdown of the simple normal-mode picture of molecular vibrations at low energies.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.